U.S. patent number 7,122,594 [Application Number 10/480,201] was granted by the patent office on 2006-10-17 for modified block copolymer composition.
This patent grant is currently assigned to Asahi Kasei Kabushiki Kaisha. Invention is credited to Nobuaki Kubo, Yasuhiro Kusanose, Toshinori Shiraki, Shigeki Takayama.
United States Patent |
7,122,594 |
Kubo , et al. |
October 17, 2006 |
Modified block copolymer composition
Abstract
A modified block copolymer composition comprising (1) 100 parts
by weight of a modified block copolymer consisting of vinyl
aromatic hydrocarbons and conjugated dienes, containing a
functional group having at least one group selected from the group
consisting of a hydroxide group, an epoxy group, an amino group, a
silanol group and an alkoxysilane group, or a hydrogenation product
of the copolymer, and (2) 0.5 to 50 parts by weight at least one of
fillers selected from the group consisting of silica-based
inorganic fillers, metal oxides and metal hydroxides is disclosed.
This modified block copolymer composition is excellent in heat
resistance, mechanical strength, transparency, abrasion resistance,
and processability.
Inventors: |
Kubo; Nobuaki (Kawasaki,
JP), Kusanose; Yasuhiro (Yokohama, JP),
Takayama; Shigeki (Tokyo, JP), Shiraki; Toshinori
(Yokohama, JP) |
Assignee: |
Asahi Kasei Kabushiki Kaisha
(Osaka, JP)
|
Family
ID: |
29267251 |
Appl.
No.: |
10/480,201 |
Filed: |
April 24, 2002 |
PCT
Filed: |
April 24, 2002 |
PCT No.: |
PCT/JP02/04090 |
371(c)(1),(2),(4) Date: |
December 10, 2003 |
PCT
Pub. No.: |
WO03/091334 |
PCT
Pub. Date: |
November 06, 2003 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20040176514 A1 |
Sep 9, 2004 |
|
Current U.S.
Class: |
524/451; 524/505;
524/494; 524/493 |
Current CPC
Class: |
C08K
3/22 (20130101); C08F 8/30 (20130101); C08K
3/36 (20130101); C08K 3/01 (20180101); C08L
53/025 (20130101); C08F 8/04 (20130101); C08L
53/005 (20130101); C08K 3/22 (20130101); C08L
53/02 (20130101); C08K 3/36 (20130101); C08L
53/025 (20130101); C08K 3/36 (20130101); C08L
53/02 (20130101); C08L 53/005 (20130101); C08L
2666/06 (20130101); C08F 8/04 (20130101); C08F
8/30 (20130101); C08F 297/04 (20130101); C08F
8/30 (20130101); C08F 297/04 (20130101); C08F
8/04 (20130101); C08F 8/42 (20130101); C08F
297/04 (20130101); C08K 3/01 (20180101); C08L
53/02 (20130101); C08L 53/025 (20130101); C08L
2666/06 (20130101); C08F 2800/20 (20130101) |
Current International
Class: |
B60C
3/04 (20060101); C08K 5/5415 (20060101) |
Field of
Search: |
;524/451,493,494,505 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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1 245 585 |
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Oct 1983 |
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EP |
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53-10945 |
|
Sep 1978 |
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JP |
|
59-131613 |
|
Jul 1984 |
|
JP |
|
62-54138 |
|
Nov 1987 |
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JP |
|
62-54140 |
|
Nov 1987 |
|
JP |
|
4-28034 |
|
May 1992 |
|
JP |
|
4-38777 |
|
Jun 1992 |
|
JP |
|
4-39495 |
|
Jun 1992 |
|
JP |
|
7-188542 |
|
Jul 1995 |
|
JP |
|
10-139963 |
|
May 1998 |
|
JP |
|
11-256025 |
|
Sep 1999 |
|
JP |
|
2001-72853 |
|
Mar 2001 |
|
JP |
|
WO 87/02369 |
|
Apr 1987 |
|
WO |
|
Primary Examiner: Harlan; Robert D.
Attorney, Agent or Firm: Birch, Stewart, Kolasch &
Birch, LLP
Claims
The invention claimed is:
1. A modified block copolymer composition comprising: (1) a
modified block copolymer consisting of a polymer block A comprising
primarily a vinyl aromatic hydrocarbon and a polymer block B
comprising primarily a conjugated diene, or a hydrogenation product
of the copolymer, and (2) at least one of fillers selected from the
group consisting of silica-based inorganic fillers, metal oxides
and metal hydroxides, wherein the molecular chain of the component
(1) has at the terminals thereof a functional group having at least
one group selected from the group consisting of a hydroxide group,
an epoxy group, an amino group, a silanol group, and an
alkoxysilane group; the component (1) has a content of the vinyl
aromatic hydrocarbon of 5 to 95% by weight; the amount of the
component (2) is 0.5 to 50 parts by weight based on 100 parts by
weight of the component (1); and the component (2) has an average
particle size in a dispersion of 0.01 to 0.3 .mu.m.
2. The modified block copolymer composition according to claim 1,
further comprising (3) an olefinic polymer, the amount of the
component (3) being 10 to 500 parts by weight based on 100 parts by
weight of the component (1).
3. The modified block copolymer composition according to claim 1 or
2, wherein the block ratio of the vinyl aromatic hydrocarbons is
not less than 50% of the whole vinyl aromatic hydrocarbons in the
component (1).
4. The modified block copolymer composition according to claim 1 or
2, wherein the component (1) is a hydrogenation product of the
modified block copolymer, the hydrogenation rate of which is not
less than 10%, and the proportion of a structural unit having a
vinyl bond to the whole structural units originated from the
conjugated dienes in the hydrogenated product being in the range of
10 to 85%, and the proportion of a 1,2C.dbd.C unit is not higher
than 15%.
5. The modified block copolymer composition according to claim 1 or
2, wherein the molecular chain of the component (1) has at the
terminals thereof a functional group selected from the group
consisting of the groups having the following formulae (1) to (14):
##STR00005## where R.sup.9, R.sup.12 to R.sup.14 are a hydrogen, a
hydrocarbon group having carbon atoms of 1 to 24, or a hydrocarbon
group having a functional group selected from the group consisting
of a hydroxide group, an epoxy group, a silanol group, and an
alkoxysilane group and having carbon atoms of 1 to 24; R.sup.10 is
a hydrocarbon chain having carbon atoms of 1 to 30, or a
hydrocarbon chain having a functional group selected from the group
consisting of a hydroxide group, an epoxy group, a silanol group,
and an alkoxysilane group and having carbon atoms of 1 to 30;
hydrocarbon groups R.sup.9, R.sup.12 to R.sup.14 and a hydrocarbon
chain R.sup.10 may have an element such as oxygen, nitrogen or
silicon bonded in the bonding form other than the hydroxide group,
the epoxy group, the silanol group, and the alkoxysilane group; and
R.sup.11 is a hydrogen or an alkyl group having carbon atoms of 1
to 8.
6. The modified block copolymer composition according to claim 1 or
2, wherein the molecular chain of the component (1) has at the
terminals thereof a functional group selected from the group
consisting of the groups having the following formulae (1) to (9):
##STR00006## where R.sup.9, R.sup.12 to R.sup.14 are a hydrogen, a
hydrocarbon group having carbon atoms of 1 to 24, or a hydrocarbon
group having a functional group selected from the group consisting
of a hydroxide group, an epoxy group, a silanol group, and an
alkoxysilane group and having carbon atoms of 1 to 24; R.sup.10 is
a hydrocarbon chain having carbon atoms of 1 to 30, or a
hydrocarbon chain having a functional group selected from the group
consisting of a hydroxide group, an epoxy group, a silanol group,
and an alkoxysilane group and having carbon atoms of 1 to 30;
hydrocarbon groups R.sup.9, R.sup.12 to R.sup.14 and a hydrocarbon
chain R.sup.10 may have an element such as oxygen, nitrogen or
silicon bonded in the bonding form other than the hydroxide group,
the epoxy group, the silanol group, and the alkoxysilane group; and
R.sup.11 is a hydrogen or an alkyl group having carbon atoms of 1
to 8.
7. The modified block copolymer composition according to claim 1 or
2, wherein the component (2) is at least one of fillers selected
from the group consisting of silica, wollastonite, montmorillonite,
zeolites, alumina, titanium oxide, magnesium oxide, zinc oxide,
slag wool, magnesium hydroxide, aluminum hydroxide, hydrated
magnesium silicate, hydrated aluminum silicate, basic magnesium
carbonate, and hydrotalcite.
8. The modified block copolymer composition according to claim 1 or
2, containing a silane coupling agent in an amount of 0.1 to 20% by
weight based on the amount of the component (2).
9. The modified block copolymer composition according to claim 7,
wherein the silica is a glass fiber.
10. The modified block copolymer composition according to claim 7,
wherein the filler is a particulate filler.
Description
TECHNICAL FIELD
The present invention relates to a thermoplastic modified block
copolymer composition comprising a functional group-containing
modified block copolymer comprising a vinyl aromatic hydrocarbon
and a conjugated diene, or its hydrogenation product, and at least
one of fillers selected from the group consisting of silica-based
inorganic fillers, metal oxides, and metal hydroxides.
Background Art
Researches have been made heretofore to produce high molecular
materials having a high performance and a high functionality by a
polymer alloy technique combining different sorts of organic high
molecular substances. For example, thermoplastic elastomer
compositions which are soft materials having rubbery properties and
do not require any vulcanizing process, and thermoplastic resin
compositions which are excellent in molding processability and
recyclability have been used in various fields including automobile
parts, domestic electrical appliance parts, wire covers, medical
instruments, footwear, miscellaneous goods, and the like. At
present, various materials as thermoplastic elastomers and
thermoplastic resins, such as polyolefins, polyurethanes,
polyesters, polystyrenes and the like, have been developed and
commercially available.
Among them, vinyl aromatic hydrocarbon-conjugated diene block
copolymers such as styrene-butadiene block copolymers and
styrene-isoprene block copolymers and the like, and their
hydrogenation products (sometimes, referred to as "hydrogenated
block copolymers" hereinafter) exhibit high pliability and good
rubber elasticity at room temperature when they have a lower
content of styrene. They are capable of producing compositions
which are excellent in molding process-ability. Moreover, when they
have a higher content of styrene, they can produce clear
thermoplastic resins having outstanding impact-resistance so that
they are useful for food packages and containers, domestic electric
appliance parts, industrial parts, utensils, toys and the like.
However, functionality and characteristics achieved by using
organic high molecular materials alone are limited, so an attempt
has been made to overcome the limitation by using a combination of
organic high molecular materials and inorganic substances depending
on applications.
For example, JP59-131613A discloses an elastomeric composition
having an improved permanent compression set which was produced by
partially cross-linking an elastomeric composition comprising
hydrogenated block copolymers, hydrocarbon oils, olefinic polymers
and inorganic tillers with organic peroxides and cross-linking
adjuvants. JP11-256025A discloses a resin composition excellent in
electric conductivity comprising polyphenylene ether resins
hydrogenated block copolymers and electroconductive inorganic
tillers. Moreover, JP2001-72853A discloses an thermoplastic resin
composition excellent in hygroscopic resistance and vibration
damping property comprising polycarbonate resins, styrene-butadiene
block copolymers and hollow ceramic particles.
However, the compositions comprising thermoplastic block copolymers
and inorganic fillers have not achieved so much improvement effect
in performance as desired because one of the two types of
components is hydrophobic organic materials while the other is
hydrophilic inorganic materials, resulting in a lower affinity with
each other and poor kneadability.
In order to improve the affinity of thermoplastic block copolymers
and different materials with one another, an attempt has been
proposed to add functional groups to the thermoplastic block
copolymers. For example, JP62-54138B and JP62-54140B disclose a
composition having an improved affinity to inorganic fillers by
adding maleic anhydride to block copolymers comprising vinyl
aromatic hydrocarbons and conjugated dienes. Moreover, JP4-39495B,
JP4-28034B and JP4-38777B disclose a composition having an improved
affinity with thermoplastic resins, tackiness imparted resins and
asphalt by adding functional groups to the terminals of block
copolymers comprising vinyl aromatic hydrocarbons and conjugated
dienes.
Under those circumstances, in conjunction with a composition
comprising a vinyl aromatic hydrocarbon-conjugated diene block
copolymer or its hydrogenated product and an inorganic material,
there has been a demanding need to provide materials having a high
performance and a high functionality which are capable of
effectively exhibiting functions and characteristics of both types
of components.
DISCLOSURE OF INVENTION
As a result of various researches to overcome the aforementioned
problems, the present inventors have completed this invention on
the basis of the findings that a composition comprising: (1) a
specifically structured modified block copolymer containing
specific functional group(s) or its hydrogenation products; and (2)
at least one of fillers selected from the group consisting of
silica-based inorganic fillers, metal oxides, and metal hydroxides;
in a specific amount of each of them is excellent in thermal
resistance, mechanical strength, transparency, abrasion resistance,
and processability. That is, the present invention is as
follows:
[1] a modified block copolymer composition comprising:
(1) a modified block copolymer consisting of a polymer block A
comprising primarily a vinyl aromatic hydrocarbon and a polymer
block B comprising primarily a conjugated diene, or its
hydrogenation products, and
(2) at least one of fillers selected from the group consisting of
silica-based inorganic fillers, metal oxides and metal
hydroxides,
wherein the molecular chain of the component (1) has at the
terminals thereof a functional group having at least one of groups
selected from the group consisting of a hydroxide group, an epoxy
group, an amino group, a silanol group, and an alkoxysilane group;
the component (1) has a content of the vinyl aromatic hydrocarbon
of 5 to 95% by weight; the amount of the component (2) is 0.5 to 50
parts by weight based on 100 parts by weight of the component (1);
and the component (2) has an average particle size in a dispersion
of 0.01 to 2 .mu.m.
[2] The modified block copolymer composition according to the above
[1], further comprising (3) an olefinic polymer, the amount of the
component (3) being 10 to 500 parts by weight based on 100 parts by
weight of the component (1).
[3] The modified block copolymer composition according to the above
[1] or [2], wherein the block ratio of the vinyl aromatic
hydrocarbon is not less than 50% of the whole vinyl aromatic
hydrocarbon in the component (1).
[4] The modified block copolymer composition according to the above
[1] or [2], wherein the component (1) is a hydrogenation product of
the modified block copolymer at the hydrogenation rate of not less
than 10%, and the proportion of a structural unit having a vinyl
bond to the whole structural units originated from the conjugated
diene in the hydrogenation products being in the range of 10 to
85%, and the proportion of a 1, 2C.dbd.C unit is not higher than
15%. [5] The modified block copolymer composition according to the
above [1] or [2], wherein the molecular chain of the component (1)
has at the terminals thereof a functional group selected from the
group consisting of the groups having the following formulae (1) to
(14):
##STR00001## where
R.sup.9, R.sup.12 to R.sup.14 are a hydrogen, a hydrocarbon group
having carbon atoms of 1 to 24, or a hydrocarbon group having a
functional group selected from the group consisting of a hydroxide
group, an epoxy group, an silanol group, and an alkoxysilane group
and having carbon atoms of 1 to 24;
R.sup.10 is a hydrocarbon chain having carbon atoms of 1 to 30, or
a hydrocarbon chain having a functional group selected from the
group consisting of a hydroxide group, an epoxy group, a silanol
group, and an alkoxysilane group and having carbon atoms of 1 to
30;
hydrocarbon groups R.sup.9, R.sup.12 to R.sup.14 and a hydrocarbon
chain R.sup.10 may have an element such as oxygen, nitrogen or
silicon bonded in the bonding form other than the hydroxide group,
the epoxy group, the silanol group, and the alkoxysilane group;
and
R.sup.11 is a hydrogen or an alkyl group having carbon atoms of 1
to 8.
[6] The modified block copolymer composition according to the above
[1] or [2], wherein the molecular chain of the component (1) has at
the terminals thereof a functional group selected from the group
consisting of the groups having the following formulae (1) to
(9):
##STR00002## where
R.sup.9, R.sup.12 to R.sup.14 are a hydrogen, a hydrocarbon group
having carbon atoms of 1 to 24, or a hydrocarbon group having a
functional group selected from the group consisting of a hydroxide
group, an epoxy group, a silanol group, and an alkoxysilane group
and having carbon atoms of 1 to 24;
R.sup.10 is a hydrocarbon chain having carbon atoms of 1 to 30, or
a hydrocarbon chain having a functional group selected from the
group consisting of a hydroxide group, an epoxy group, a silanol
group, and an alkoxysilane group and having carbon atoms of 1 to
30;
hydrocarbon groups R.sup.9, R.sup.12 to R.sup.14 and a hydrocarbon
chain R.sup.10 may have an element such as oxygen, nitrogen or
silicon bonded in the bonding form other than the hydroxide group,
the epoxy group, the silanol group, and the alkoxysilane group;
and
R.sup.11 is a hydrogen or an alkyl group having carbon atoms of 1
to 8.
[7] The modified block copolymer composition according to the above
[1] or [2], wherein the component (2) is at least one of fillers
selected from the group consisting of silica, wollastonite,
montmorillonite, zeolites, alumina, titanium oxide, magnesium
oxide, zinc oxide, slag wool, glass fibers, magnesium hydroxide,
aluminum hydroxide, hydrated magnesium silicate, hydrated aluminum
silicate, basic magnesium carbonate, and hydrotalcite. [8] The
modified block copolymer composition according to the above [1] or
[2], containing a silane coupling agent in an amount of 0.1 to 20%
by weight based on the amount of the component (2).
BEST MODE FOR CARRYING OUT THE INVENTION
As described above, the present invention relates to a new
characteristic material having a combination of the advantages of
organic high molecular substances (e.g., light weight, softness,
moldability and the like) and those of inorganic substances (e.g.,
thermal resistance, high strength and the like). Among other
things, in connection with a composition containing a modified
block copolymer comprising a vinyl aromatic hydrocarbon and a
conjugated diene, or its hydrogenation products, and at least one
of fillers selected from the group consisting of silica-based
inorganic fillers, metal oxides and metal hydroxides, the present
invention provides materials having a high performance and a high
functionality which can effectively manifest the functionalities
and the characteristics of the both components
The modified block copolymer to be used in the present invention
consists of a polymer block A comprising primarily a vinyl aromatic
hydrocarbon and a polymer block B comprising primarily a conjugated
diene, wherein the molecular chain of said modified block copolymer
has at the terminals thereof a functional group having at least one
of groups selected from the group consisting of a hydroxide group,
an epoxy group, an amino group, a silanol group and an alkoxysilane
group.
For example, there can be provided a modified block copolymer by
reacting a block copolymer consisting of a polymer block A
comprising primarily a vinyl aromatic hydrocarbon and a polymer
block B comprising primarily a conjugated diene with a modifying
agent as described below through an addition reaction to bond the
agent to the living terminals of the block copolymer, or the
hydrogenation product thereof. The modified block copolymer
obtained by this method has a structure expressed, for example, by
one of the following general formulae: (A--B).sub.n--X,
(B--A).sub.n--X, A--(B--A).sub.n--X, B--(A--B).sub.n--X,
X--(A--B).sub.n--X, X--A--(B--A).sub.n--X, X--B--(A--B).sub.n--X,
[(B--A)n].sub.m--X, [(A--B)n].sub.m--X, [(B--A)n-B].sub.m--X,
[(A--B)n-A].sub.m--X where
A represents a polymer block comprising primarily a vinyl aromatic
hydrocarbon, and B represents a polymer block comprising primarily
a conjugated diene,
n is an integer of 1 or more, generally 1 to 5, and m is an integer
of 2 or more, generally 2 to 10.
X is a modifying agent's residue having a functional group as
described below.
The polymer block A comprising primarily a vinyl aromatic
hydrocarbon in the present invention represents a copolymer block
comprising a vinyl aromatic hydrocarbon and a conjugated dienes,
which contains 50% by weight or more, preferably 70% by weight or
more of a vinyl aromatic hydrocarbon, and/or a homopolymer block of
a vinyl aromatic hydrocarbon. The polymer block B comprising
primarily a conjugated diene represents a copolymer block
comprising a conjugated diene and a vinyl aromatic hydrocarbon,
which contains more than 50% by weight, preferably 60% by weight or
more of a conjugated diene, and/or a homopolymer block of a
conjugated diene. The vinyl aromatic hydrocarbon units may be
distributed uniformly or in a tapered form in the copolymer blocks.
The copolymer blocks may have a plurality of regions where the
vinyl aromatic hydrocarbon units are distributed uniformly and/or a
plurality of regions where the units are distributed in the tapered
form.
The modified block copolymers to be used in the present invention
may be an optional mixture of the modified block copolymers as
expressed by the aforementioned general formulae.
As processes for producing the block copolymers before being
modified (sometimes referred to simply as "block copolymer"
hereinafter), those as disclosed in, e.g., JP43-17979B,
JP49-36957B, JP48-4106B, and JP59-166518A may be mentioned.
The vinyl aromatic hydrocarbons to be used in the present invention
include, e.g., styrene, o-methylstyrene, p-methylstyrene,
p-tert-butylstyrene, 1,3-dimethylstyrene, .alpha.-methylstyrene,
vinylnaphthalene, vinyl anthracene and the like and a combination
of two or more thereof, with styrene being generally used. The
conjugated dienes to be used in the present invention include,
e.g., 1,3-butadiene, 2-methyl -1,3-butadiene (isoprene),
2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene and the
like, and a combination of two or more thereof with 1,3-butadiene
and isoprene being generally used.
Solvents to be used in the production of the block copolymers of
the present invention include, e.g., aliphatic hydrocarbons such as
butane, pentane, hexane, isopentane, heptane, octane, and
isooctane; alicyclic hydrocarbons such as cyclopentane,
methylcyclopentane, cyclohexane, methylcyclohexane, and
ethylcyclohexane; and aromatic hydrocarbons such as benzene,
toluene, ethylbenzene, and xylene. These solvents may be used alone
or in a combination of two or more.
Polymerization initiators to be used in the production of the block
copolymers include organic lithium compounds. The organic lithium
compounds are those having one or more of lithium atoms in a
molecule. For example, mention may be made of ethyl lithium,
n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl
lithium, tert-butyl lithium, hexamethylene dilithium, butadienyl
dilithium, isoprenyl dilithium, and the like. These initiators may
be used alone or in a combination of two or more. The organic
lithium compounds may be added in portions in the course of the
production (polymerization) of the block copolymers
In the present invention, polar compounds and randomizing agents
may be used for the purposes of controlling the polymerization rate
in the production of the block copolymers, the micro-structures of
the polymerized conjugated diene moieties, and the occurrence of a
random copolymerization of conjugated dienes and vinyl aromatic
hydrocarbons. The polar compounds and the randomizing agents
include ethers, amines, thioethers, phosphines, phosphoramides,
potassium or sodium salts of alkylbenzene sulfonates, alkoxydes of
potassium or sodium and the like. Practically examples of the
ethers include dimethyl-ether, diethylether, diphenylether,
tetrahydrofuran, diethyleneglycol dimethylether, and
diethyleneglycol dibutylether. The amines include tertiary amines,
trimethylamine, triethylamine, tetramethylethylene diamine, and
other cyclic tertiary amines. The phosphines and phosphoramines
include triphenylphosphine, hexamethylphosphoramide, and the
like.
The polymerization temperature in the production of the block
copolymers according to the present invention is preferably -10 to
150.degree. C., more preferably 30 to 120.degree. C. Although it
depends upon reaction conditions, the polymerization period is
preferably within 48 hours, particularly preferably 0.5 to 10
hours. The polymerization system should be preferably in the
atmosphere of inert gas, such as nitrogen gas. The polymerization
pressure is not critical, provided that it is a pressure in the
range enough to keep the monomers and the solvents in a liquid
phase within the aforementioned polymerization temperature range.
Moreover, it should preferably be in mind that impurities making
the catalysts and the living polymers inactive, such as water,
oxygen, carbon dioxide gas and the like should be prevented from
introducing into the polymerization system.
The component (1), i.e., the modified block copolymer and its
hydrogenation products to be used in the present invention is a
modified block copolymer which has a functional group having at
least one of groups selected from the group consisting of a
hydroxide group, an epoxy group, an amino group, a silanol group
and an alkoxysilane group bonded to the terminals of its molecular
chain, or its hydrogenation products. As a process for producing
those modified block copolymers having such functional groups, as
described above, a process of reacting the block copolymer at its
living terminal(s) with a modifying agent having the aforementioned
functional group(s) or with a modifying agent having the
aforementioned functional groups protected by a known technique may
be mentioned. Although there may be a case where the hydroxide
group and the amino group are in the form of organic metal salt
after the modifying agents were reacted depending upon the kinds
thereof, in such a case, they can be converted to a hydroxide group
and an amino group by treating with a compound containing an active
hydrogen such as water and alcohols.
In the present invention, after the block copolymers were subjected
at their living terminals to the reaction with modifying agents,
there might be remained a part of unmodified block copolymers in a
mixture. The unmodified block copolymers may be present in the
mixture with the modified block copolymers in a proportion of,
preferably not higher than 60% by weight, more preferably not
higher than 50% by weight.
Examples of the functional groups having at least one of groups
selected from the group consisting of a hydroxide group, an epoxy
group, an amino group, a silanol group, and an alkoxysilane group
include those selected from the group consisting of functional
groups represented by the following general formulae (1) to
(14):
##STR00003## where
R.sup.9, R.sup.12 to R.sup.14 are a hydrogen, a hydrocarbon group
having carbon atoms of 1 to 24, or a hydrocarbon group having a
functional group selected from the group consisting of a hydroxide
group, an epoxy group, a silanol group, and an alkoxysilane group
and having carbon atoms of 1 to 24;
R.sup.10 is a hydrocarbon chain having carbon atoms of 1 to 30, or
a hydrocarbon chain having a functional group selected from the
group consisting of a hydroxide group, an epoxy group, a silanol
group, and an alkoxysilane group and having carbon atoms of 1 to
30;
hydrocarbon groups R.sup.9, R.sup.12 to R.sup.14 and hydrocarbon
chain R.sup.10 may have an element such as oxygen, nitrogen or
silicon bonded in the bonding form other than the hydroxide group,
the epoxy group, the silanol group, and the alkoxysilane group;
and
R.sup.11 is a hydrogen or an alkyl group having carbon atoms of 1
to 8.
The modifying agents to be used for producing the modified block
copolymers of the present invention include, e.g., tetraglycidyl
m-xylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane,
tetraglycidyl-p-phenylenediamine,
tetraglycidyldiamino-diphenylmethane, diglycidylaniline,
diglycidylorthotoluidine, .gamma.-glycidoxyethyl-trimethoxysilane,
.gamma.-glycidoxypropyl trimethoxysilane, .gamma.-glycidoxybutyl
trimethoxysilane, .gamma.-glycidoxypropyl triethoxysilane,
.gamma.-glycidoxypropyl tripropoxysilane, .gamma.-glycidoxypropyl
tributoxysilane, .gamma.-glycidoxypropyl triphenoxysilane,
.gamma.-glycidoxypropyl methyldimethoxysilane,
.gamma.-glycidoxypropyl ethyldimethoxysilane,
.gamma.-glycidoxypropyl ethyldiethoxysilane,
.gamma.-glycidoxypropyl methyldiethoxysilane,
.gamma.-glycidoxypropyl methyldipropoxysilane,
.gamma.-glycidoxypropyl methyldibutoxysilane,
.gamma.-glycidoxypropyl methyldiphenoxysilane,
.gamma.-glycidoxypropyl dimethylmethoxysilane,
.gamma.-glycidoxypropyl diethylethoxysilane,
.gamma.-glycidoxypropyl dimethylethoxysilane,
.gamma.-glycidoxypropyl dimethylphenoxysilane,
.gamma.-glycidoxypropyl diethylmethoxysilane,
.gamma.-glycidoxypropyl methyldiisopropeneoxysilane,
bis(.gamma.-glycidoxypropyl)dimethoxysilane,
bis(.gamma.-glycidoxypropyl)diethoxysilane,
bis(.gamma.-glycidoxypropyl)dipropoxysilane,
bis(.gamma.-glycidoxypropyl)dibutoxysilane,
bis(.gamma.-glycidoxypropyl)diphenoxysilane,
bis(.gamma.-glycidoxypropyl)methylmethoxysilane,
bis(.gamma.-glycidoxypropyl)methylethoxysilane,
bis(.gamma.-glycidoxypropyl)methylpropoxysilane,
bis(.gamma.-glycidoxypropyl)methylbutoxysilane,
bis(.gamma.-glycidoxypropyl)methylphenoxysilane,
tris(.gamma.-glycidoxypropyl)methoxysilane,
.gamma.-methacryloxypropyl trimethoxysilane,
.gamma.-methacryloxypropyl triethoxysilane,
.gamma.-methacryloxymethyl trimethoxysilane,
.gamma.-methacryloxyethyl triethoxysilane,
bis(.gamma.-methacryloxypropyl)dimethoxysilane,
tris(.gamma.-methacryloxypropyl)methoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-triethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-tripropoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-tributoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-triphenoxysilane,
.beta.-(3,4-epoxycyclohexyl)propyl-trimethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-methyldimethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-ethyldimethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-ethyldiethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-methyldiethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-methyldipropoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-methyldibutoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-methyldiphenoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-dimethylmethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-diethylethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-dimethylethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-dimethylpropoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-dimethylbutoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-dimethylphenoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-diethylmethoxysilane,
.beta.-(3,4-epoxycyclohexyl)ethyl-methyldiisopropeneoxy-silane,
1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone,
N,N'-dimethylpropyleneurea, and N-methylpyrrolidone.
The reaction with the aforementioned modifying agents can produce
the modified block copolymers comprising the polymer block A and/or
the polymer block B to which the residue of the modifying agents,
i.e., a functional group selected from the group consisting of a
hydroxide group, an epoxy group, an amino group, a silanol group,
and an alkoxysilane group is bonded, or the hydrogenation products
of the modified block copolymers. The sites of the modified block
copolymers, to which the residue of the modifying agents is bonded,
are not critical, though it is preferred that it is bonded to the
polymer block A to achieve a composition having excellent physical
properties at high temperatures.
The amount of the modifying agents containing functional groups to
be used for the addition reaction with the living terminals of the
block copolymers in the present invention should be preferably
higher than 0.5 equivalent, more preferably higher than 0.7
equivalent, and most preferably higher than 0.9 equivalent based on
one equivalent of the living terminals of the block copolymers,
while it should be preferably not higher than 10 equivalents, more
preferably not higher than 5 equivalents, and most preferably not
higher than 4 equivalents based on one equivalent of the living
terminals of the block copolymers.
The amount of the living terminals of the block copolymers in the
present invention can be calculated from the amount of organic
lithium compounds used in the polymerization and the number of
lithium atoms bonded to the organic lithium compounds.
The hydrogenation products of the modified block copolymers of the
present invention can be obtained by hydrogenating the modified
block copolymers produced by the aforementioned process.
Hydrogenation catalysts to be used for the hydrogenation are not
critical and may be as conventionally known catalysts (i)
heterogeneous supported catalysts such as Ni, Pt, Pd, and Ru metals
on the supports of carbon, silica, alumina diatomaceous earth or
the like, (ii) so-called Ziegler hydrogenation catalysts employing
transition metal salts such as organic acid salts or
acetylacetonates of Ni, Co, Fe, or Cr and a reducing agent such as
organic aluminum, (iii) homogeneous hydrogenation catalysts such as
so-called organic metal complexes, e.g., organic metal compounds of
Ti, Ru, Rh, Zr, or the like.
In practice those hydrogenation catalysts as disclosed in
JP42-8704B, JP43-6636B, JP63-4841B, JP1-37970B, JP1-53851B, and
JP2-9041B may be useful. Preferred hydrogenation catalysts include
a mixture of titanocene compounds and reducing organic metal
compounds.
The titanocene compounds as those disclosed in JP8-109219A may be
used, though practically a compound containing at least one of
ligands having a substituted or unsubstituted cyclopentadienyl
skeleton, an indenyl skeleton, or a fluorenyl skeleton such as
biscyclopentadienyl titanium dichloride, or
monopentamethylcyclopentadienyl titanium trichloride may be
mentioned. The reducing organic metal compounds include organic
alkali metal compounds such as organic lithium, organic magnesium
compounds, organic aluminum compounds, organic boron compounds, or
organic zinc compounds.
The hydrogenation reaction is performed generally in the
temperature range of 0 to 200.degree. C., preferably 30 to
150.degree. C. The hydrogen pressure to be used in the
hydrogenation reaction ranges from 0.1 to 15 MPa, preferably from
0.2 to 10 MPa, more preferably from 0.3 to 5 MPa. The hydrogenation
reaction time ranges from 3 minutes to 10 hours, preferably 10
minutes to 5 hours. The hydrogenation reaction may be conducted in
a batch process, a continuous process, or in a combination
thereof.
The structural units originated from the conjugated dienes in the
hydrogenation products of the modified block copolymers can be
represented by the following general formulae (a) to (e):
##STR00004## where
R.sup.1 to R.sup.8 represents independently a hydrogen, a halogen,
an aliphatic hydrocarbon having carbon atoms of 1 to 20, or an
aromatic hydrocarbon having carbon atoms of 1 to 20, and they may
be identical to or different from one another;
the formula (a) represents a cis-structure, and
the formula (b) represents a trans-structure.
The hydrogenation rate of the hydrogenated modified block
copolymers should be preferably not less than 10%, more preferably
30 to 100%, most preferably 50 to 100% from the point of view of
achieving a composition having good thermal stability. The
hydrogenation rate of the hydrogenated modified block copolymers
may be expressed by the following equation on the basis of the
above formulae (a) to (e). Hydrogenation
rate=(c+e)/(a+b+c+d+e).times.100
Moreover, the proportion of the structural units having a vinyl
bond to the whole structural units originated from the conjugated
dienes in the hydrogenated modified block copolymers should be
preferably in the range from 10 to 85%, more preferably 30 to 75%,
most preferably 35 to 70% from the point of view of the
productivity of the block copolymers and the softness and the
impact resistance of the resulting compositions. The proportion of
the structural units having a vinyl bond to the whole structural
units originated from the conjugated dienes can be expressed by the
following equation on the basis of the above formulae (a) to (e).
Proportion of vinyl bonds=(d+e)/(a+b+c+d+e).times.100
Furthermore, the proportion of the 1,2C.dbd.C units to the whole
structural units originated from the conjugated dienes in the
hydrogenated modified block copolymers should be preferably in the
range not higher than 15%, more preferably 0 to 7%, most preferably
0 to 3% from the point of view of achieving a composition having a
good thermal stability. The proportion of the 1,2C.dbd.C units
based on the total structural units originated from the conjugated
dienes can be expressed by the following equation on the basis of
the above formulae (a) to (e): Proportion of 1,2C.dbd.C
units=d/(a+b+c+d+e).times.100
The content of the vinyl aromatic hydrocarbons in the modified
block copolymers or the hydrogenation products thereof as described
above can be determined by using a ultraviolet spectrophotometer
and the like. The proportion of the structural units having a vinyl
bond to the whole structural units originated from the conjugated
dienes in the hydrogenated modified block copolymers and the
hydrogenation rate of the hydrogenated modified block copolymers
can be determined by using a nuclear magnetic resonance (NMR)
system. Alternatively, the content of the vinyl aromatic
hydrocarbons in the hydrogenated modified block copolymers may be
grasped as the content of the vinyl aromatic hydrocarbons in the
copolymers before the hydrogenation.
The final modified block copolymers or the hydrogenation products
thereof can be obtained by removing the catalyst residue from a
solution of the modified block copolymers or the hydrogenation
products thereof produced by the aforementioned processes, as
required, and separating the solvents. As processes for separating
the solvents, there may be mentioned, e.g., a process comprising
adding a polar solvent such as acetone or alcohol, which is a poor
solvent for the polymer, to the polymer solution resulting in
precipitation of the polymer and then recovering the polymer; a
process comprising pouring the polymer solution into a hot water
with stirring and stripping with steam to remove the solvent and
recovering the polymer; or a process comprising heating directly
the polymer solution to evaporate and remove the solvent.
Stabilizers which may be added to the modified block copolymers
used in the present invention or the hydrogenation products thereof
include various phenolic stabilizers, phosphorus-based stabilizers,
sulfur-based stabilizers, and amine-based stabilizers.
The content of the vinyl aromatic hydrocarbons in the component (1)
used in the present invention should be from 5 to 95% by weight,
preferably 8 to 80% by weight, more preferably 10 to 70% by weight.
If it is lower than 5% by weight, the resulting composition is
undesirably poor in permanent compression set and tensile strength,
while if it is higher than 95% by weight, the resulting composition
is undesirably reduced in impact resistance. In case the content of
the vinyl aromatic hydrocarbons is generally not higher than 60% by
weight, specifically not higher than 55% by weight, the component
(1) exhibits characteristics as a thermoplastic elastic body, while
in case it is generally higher than 60% by weight, specifically 65%
by weight or higher, the component (1) exhibits characteristics as
a thermoplastic resin.
The component (1) should preferably have a weight average molecular
weight of 30,000 or more from the standpoint of tensile strength of
the composition, 1,000,000 or less from the standpoint of
processability, more preferably 60,000 to 800,000, still more
preferably 70,000 to 600,000. The weight average molecular weight
may be determined from the peak molecular weight shown in a
chromatogram obtained by using a gel permeation chromatography
(GPC) on the basis of a calibration curve which is obtained from
measurements with commercially available standard polystyrenes
(which is drawn by using the peak molecular weight of a standard
polystyrene).
The component (1) should have a block ratio of the vinyl aromatic
hydrocarbons of not less than 50%, preferably 50 to 97% by weight,
still more preferably 60 to 95% by weight based on the whole vinyl
aromatic hydrocarbons in the component (1) to produce a composition
being excellent in permanent compression set. The block ratio of
vinyl aromatic hydrocarbons refers here to a proportion of the
vinyl aromatic hydrocarbon polymer blocks present in the component
(1).
The block ratio of the vinyl aromatic hydrocarbons can be
determined by using the vinyl aromatic hydrocarbon polymer block
components obtained through oxidation decomposition of the block
copolymer with tertiary butyl hydroperoxide on an osmium
tetrachloride catalyst (which is a process as disclosed in I. M.
KOLTHOFF, et al., J. Polym. Sci. 1,429 (1946)), except that the
vinyl aromatic hydrocarbon polymer block component having a degree
of polymerization of about 30 or less is excluded, according to the
following equation. Block ratio of Vinyl Aromatic Hydrocarbons
(%)=[(Mass of Vinyl aromatic hydrocarbon polymer blocks in Block
copolymer)/(Mass of Whole Vinyl aromatic hydrocarbons in Block
copolymer)].times.100
Next, fillers to be used as the component (2) in the present
invention will be described. The component (2) is at least one of
fillers selected from the group consisting of silica-based
inorganic fillers, metal oxides, and metal hydroxides.
The silica-based inorganic fillers refers here to solid particles
comprising primarily SiO.sub.2 or Si.sub.3Al as structural units.
For example, silica, clay, talc, micas, wollastonite,
montmorillonite, zeolites, and inorganic fiber materials such as
glass fibers can be employed. Moreover, silica-based inorganic
fillers having the surfaces made hydrophobic, a combination of two
or more of the silica-based inorganic fillers, and a mixture of the
silica-based inorganic fillers with non-silica-based inorganic
fillers may be used. Silicas which can be used include those such
as so-called anhydrous white carbons, hydrous white carbons,
synthetic silicate white carbons, and colloidal silica.
The metal oxides refers to solid particles comprising primarily
structural units expressed by the chemical formula M.sub.xO.sub.y
where M is a metal atom and each of x and y is an integer of 1 to
6, such as alumina, titanium oxide, magnesium oxide, and zinc
oxide. A combination of two or more of metal oxides and a mixture
of the metal oxides with inorganic fillers other than the metal
oxides may be used.
The metal hydroxides which can be used refers to hydrated inorganic
fillers such as aluminum hydroxide, magnesium hydroxide, zirconium
hydroxide, hydrated aluminum silicate, hydrated magnesium silicate,
basic magnesium carbonate, hydrotalcite, calcium hydroxide, barium
hydroxide, hydrated tin oxide, hydrates of inorganic metal
compounds such as borax. A combination of two or more of metal
hydroxides and a mixture of the metal hydroxides with inorganic
fillers other than the metal hydroxides may be used.
The fillers to be used in the present invention should preferably
be silica and glass fibers with silica being particularly
preferred.
In the present invention, the fillers should have an average
particle size in a dispersion of, preferably 0.01 to 2 .mu.m, more
preferably 0.03 to 1 g m, most preferably 0.05 to 0.5 .mu.m from
the standpoint of dispersing the fillers in a composition and
developing sufficiently the effects of the fillers to be added. The
average particle size of the fillers in a dispersion can be
determined by observing the state of dispersion of the fillers with
a transmission electron microscope (TEM) and using an image
analyzer.
The amount of the component (2) should be 0.5 to 50 parts by
weight, preferably 3 to 40 parts by weight based on 100 parts by
weight of the component (1). When the amount of the component (2)
to be incorporated is less than 0.5 part by weight, the fillers can
not exhibit an effect of addition, while when it is higher than 50
parts by weight, the component (2) is poorly dispersed and the
processability and mechanical strength become undesirably
reduced.
The composition of the present invention may further contain an
olefinic polymer (sometimes referred to as a component (3)
hereinunder) in addition to the aforementioned components (1) and
(2). As the olefinic polymers, there may be mentioned those as
comprising primarily .alpha.-olefins such as ethylene, propylene
and the like, for example, polyethylenes, polypropylenes,
ethylene-propylene copolymers, chlorinated polyethylenes and the
like. The olefinic polymers to be used may include those as
copolymerized with a small amount of vinyl monomers in addition to
the olefins such as ethylene, propylene and the like. For example,
ethylene-vinyl acetate copolymers, ethylene-(meth)acrylic acid
copolymers, ethylene-(meth)acrylic acid derivative copolymers and
the like may be mentioned. Moreover, the olefinic polymers may
include also hydrogenation products of polymers comprising
conjugated diene monomers such as butadiene, isoprene and the like.
These resins may be used in a mixture of two or more of them. The
polypropylenes, or the mixture of polypropylenes and
ethylene-propylene copolymers are preferred in view of the
processability and the mechanical properties of the resulting
compositions.
The amount of the component (3) should be preferably 10 to 500
parts by weight, more preferably 20 to 300 parts by weight based on
100 parts by weight of the component (1) in view of the balance
between the permanent compression set, the tensile strength and the
elasticity of the composition.
In the modified block copolymer composition of the present
invention, the component (1), i.e., the modified block copolymers
or the hydrogenation products thereof contain specific functional
groups so that they have a high affinity to the component (2),
fillers, allowing the fillers to finely disperse in the copolymers
while exhibiting effectively interaction therebetween due to
chemical bonds such as hydrogen-bonds. Thus, it is possible to
achieve the objects of the present invention that the modified
block copolymer composition being excellent in heat resistance,
mechanical strength, transparency, abrasion resistance, and
processability can be produced. Moreover, it is also possible to
produce a modified block copolymer composition which is excellent
in permanent compression set, impact resistance and
processability.
The modified block copolymer composition of the present invention
may further contain silane coupling agents incorporated. The silane
coupling agents are for rendering the interaction between the
components (1) and (2) more intimate and contain a group having an
affinity or a bonding property to the component (1) and/or the
component (2). The silane coupling agents to be used may include
those as generally used for inorganic fillers such as silica, for
example, 3-mercaptopropyl-trimethoxysilane,
3-mercaptopropylmethyldimethoxysilane, vinyltrimethoxysilane,
vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
3-glycidoxypropyl methyldiethoxysilane, 3-glycidoxypropyl
triethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl
methyldimethoxysilane, 3-methacryloxypropyl trimethoxysilane,
3-methacryloxypropyl methyldiethoxysilane, 3-methacryloxypropyl
triethoxysilane, 3-acryloxypropyl trimethoxysilane,
N-2(aminoethyl)3-aminopropyl methyldimethoxysilane,
N-2(aminoethyl)3-aminopropyl trimethoxysilane,
N-2(aminoethyl)3-aminopropyl triethoxysilane, 3-aminopropyl
trimethoxysilane, 3-aminopropyl triethoxysilane,
3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine,
N-phenyl-3-aminopropyl trimethoxysilane, and 3-isocyanatepropyl
triethoxysilane.
Particularly preferred silane coupling agents in the present
invention are those as having a polysulfide linkage connecting two
or more of mercapto groups and/or sulfur atoms together with a
silanol group or an alkoxysilane group. Such silane coupling agents
include, for example, 3-mercaptopropyltrimethoxysilane,
3-aminopropyltriethoxysilane,
bis-[3-(triethoxysilyl)-propyl]-tetrasulfide,
bis-[3-(triethoxysilyl)-propyl]-disulfide,
bis-[3-(triethoxysilyl)-propyl]-trisulfide,
bis-[2-(triethoxysilyl)-ethyl]-tetrasulfide,
3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide,
3-trimethoxysilylpropyl-N,N-dimethyl-thiocarbamoyl tetrasulfide,
3-triethoxysilylpropylbenzothiazole tetrasulfide, and
3-trimethoxysilylpropylbenzothiazole tetrasulfide.
The amount of the silane coupling agents to be incorporated should
be preferably 0.1 to 20% by weight, more preferably 0.5 to 18% by
weight, still more preferably 1 to 15% by weight based on the
amount of the component (2) in order to sufficiently exhibit
reinforced effects by the fillers.
The silane coupling agents may be used in combination with sulfur
and organic peroxides.
The modified block copolymer composition of the present invention
may further be formulated with block copolymers, or the
hydrogenation products thereof, which are different from the
modified block copolymers or the hydrogenation products thereof to
be used in the present invention, such as non-modified block
copolymers, thermoplastic resins, rubbery polymers and the
like.
The thermoplastic resins include block copolymer resins of vinyl
aromatic compounds with conjugated dienes which are different from
the modified block copolymers or the hydrogenation products thereof
defined in the present invention; vinyl aromatic compound resins
such as polystyrenes; copolymer resins of vinyl aromatic compounds
with other vinyl monomers, such as ethylene, propylene, butylene,
vinyl chloride, vinilidene chloride, vinyl acetate, acrylic acid
and acrylate esters such as methyl acrylate, methacrylic acid and
methacrylate esters such as methyl methacrylate, acrylonitrile, or
methacrylonitrile; rubber-modified styrene resins (HIPS);
acrylonitrile-butadiene-styrene-copolymer resins (ABS);
methacrylate ester-butadiene-styrene-copolymer resins (MBS);
poly(vinyl acetate) resins, i.e., copolymers comprising vinyl
acetate with other monomers polymerizable therewith and having a
content of vinyl acetate of 50% by weight or more, and the
hydrolysis products of the resins; polymers of acrylic acid and its
esters and/or amido; polymers of methacrylic acid and its esters
and/or amido; polyacrylate resins, i.e., copolymers of 50% by
weight or more of the aforementioned acrylic monomers with other
copolymerizable monomers; polymers of acrylonitrile and/or
methacrylonitrile; nitril resins i.e., copolymers of 50% by weight
or more of the aforementioned acrylonitrile monomers with other
copolymerizable monomers; aliphatic polyamide resins such as
nylon-46, nylon-6, nylon-66, nylon-610, nylon-11, nylon-12, or
nylon-6-nylon-12 copolymer; aromatic polyamide resins such as
polyphenyleneisophthalamide, polyphenyleneterephthalamide, or
polymetaxylenediamine; polyester resins such as condensation
polymers of dibasic acids such as adipic acid, sebacic acid,
terephthalic acid, isophthalic acid, P,P'-dicarboxydiphenyl,
2,6-naphthalenedicarboxylic acid, or derivatives therefrom with
glycol (or diol) components such as ethylene glycol, propylene
glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol,
P-xylene glycol, or bisphenol A; polyesterdiols such as
poly(1,4-butyleneadipate), poly(1,6-hexaneadipate), or
polycaprolactone; polyetherdiols such as polyethylene glycols,
polypropylene glycols, or polyoxytetramethylene glycols;
thermoplastic polyurethane polymers produced by a polyaddition
reaction of glycol components selected from glycols such as
ethylene glycol, 1,4-butanediol, and 1,6-hexanediol with
diisocyanate components such as tolylenediisocyanate,
4,4'-diphenylmethanediisocyanate, or hexamethylenediisocyanate;
polycarbonate polymers such as
poly-4,4'-dioxydiphenyl-2,2'-propanecarbonate; polysulfone resins
such as poly(ethersulfone), poly(4,4'-bisphenolethersulfone), and
poly(thioethersulfone); polymers of formaldehyde or trioxane;
polyoxymethylene resins such as copolymers of formaldehyde or
trioxane with other aldehyde, cyclicether, epoxide, isocyanate, or
vinyl compounds; polyphenylene ether resins such as
poly(2,6-dimethyl-1,4-phenylene)ether; polyphenylenesulfide resins
such as polyphenylenesulfides, or poly4,4'-diphenylenesulfides;
polyimides, polyaminobismaleimides (polybismaleimides),
bismaleimide-triazine resins; polyimide resins such as
polyamidoimido, and polyetherimido.
Those thermoplastic resins should have a number average molecular
weight of preferably not less than 1,000, more preferably 5,000 to
5,000,000, still more preferably 10,000 to 1,000,000.
Optionally, a combination of two or more of those thermoplastic
resins may be used.
The rubbery polymers include butadiene rubbers and the
hydrogenation products thereof, styrene-butadiene rubbers and the
hydrogenation products thereof which are different from the
modified block copolymers and the hydrogenation products thereof
defined in the present invention, isoprene rubbers,
acrylonitrile-butadiene rubbers and the hydrogenation products
thereof, chloroprene rubbers, ethylene-propylene rubbers,
ethylene-propylene-diene rubbers, ethylene-butene-diene rubbers,
butyl rubbers, ethylene-butene rubbers, ethylene-hexene rubbers,
ethylene-octene rubbers, acrylic rubbers, fluororubbers, silicone
rubbers, chlorinated polyethylene rubbers, epichlorohydrin rubbers,
.alpha., .beta.-unsaturated nitril-acrylate ester-conjugated diene
copolymer rubbers, urethane rubbers, polysulfide rubbers,
styrene-butadiene block copolymers and the hydrogenation products
thereof, styrene-isoprene block copolymers, and natural rubbers.
Those rubbery polymers may be modified rubbers having functional
groups attached.
Among the thermoplastic resins and rubbery polymers as described
above, most preferably, polystyrene resins and polyphenyleneether
resins may be mentioned.
Moreover, optional additives may be incorporated depending upon
various end uses as long as they do not adversely affect the
effects of the present invention. The type of the additives is not
critical, provided that they have been generally used for
formulation of thermoplastic resins and rubbery polymers.
For example, rubber softening agents such as naphthenic and/or
paraffinic, or polybutenes, low molecular weight polybutadienes,
paraffins, organic polysiloxanes, and mineral oils; inorganic
fillers such as calcium carbonate, magnesium carbonate, calcium
sulfate, and barium sulfate; pigments such as carbon black and iron
oxides; lubricants such as stearic acid, behenic acid, zinc
stearate, calcium stearate, magnesium stearate, and ethylene
bis-stearoamide; releasing agents; plasticizers; antioxidants such
as hindered phenolic antioxidants, and phosphorus-containing
thermal stabilizers; hindered amine photostabilizers; benzotriazole
ultraviolet absorbers; flame retardants; electrostatic inhibitors;
reinforcing agents such as organic fibers, glass fibers, carbon
fibers, and metal whiskers; colorants; other additives and a
combination thereof; and those as described in "Agents for
Rubber-Plastic Formulation" (Edited by Rubber Digest-Sha Co., Ltd.)
may be mentioned.
Processes for producing the modified block copolymer composition of
the present invention are not critical, and any one of known
processes may be employed.
For example, the production may be made by using a melt kneader
such as a single screw extruder, twin screw extruder, Banbury
mixer, heating rolls, Brabender, and various kneaders. In the
production, the components may be incorporated in any order, for
example, all the components may be kneaded in one time, or optional
components may be kneaded and then the remaining components may be
added sequentially or in one portion with kneading.
In one embodiment, the production may be conducted by dispersing
the component (2) in a solution obtained after the component (1)
was polymerized or after the hydrogenation reaction was effected,
or in a solution obtained by dissolving the component (1) in a
solvent, mixing the whole, and then heating the mixture to remove
the solvents.
In the present invention, the melt kneading process with an
extruder is preferred in view of productivity, though the mixing in
the solvent is specifically recommended in order to produce a
highly dispersible composition.
The modified block copolymer composition of the present invention
is capable of developing an composite state through a unification
of the specific functional groups (as described above) contained in
the modified block copolymers or the hydrogenation products thereof
with the fillers due to chemical bonding such as hydrogen bonding
therebetween. This development of the composite state can be
confirmed by the fact that when the components (1) and (2) are
mixed in a solution, or when the component (2) is added to a
solution of the component (1) and then mixed, few proportion of the
component (2) is separated and settled from the mix solution even
after standing for a certain period of time with a major proportion
being floated in a fine dispersion. Particularly in case the
component (2) has a small average particle size (for example, a
secondary particle size of less than 50 .mu.m), the existence of
the component (2) settled on the bottom of a vessel is
substantially nearly undiscernable. On the other hand, in case the
component (1) does not have any functional groups as defined in the
present invention, almost all the component (2) is settled down on
the bottom of a vessel from a solution of a mixture of the
component (1) with the component (2) after leaving to stand for a
certain period of time.
The block copolymer composition of the present invention can be
shaped with conventional thermoplastic resin molding machines. It
can be used as various molded articles such as sheet, film, various
forms of injection-molded articles, blow-molded articles,
pressure-formed shapes, vacuum-molded articles, extrusion-molded
articles and the like. Those molded articles can be used for food
packaging materials, medical instrument materials, domestic
appliances and parts thereof, materials for automobile parts,
industrial products, daily goods, toys and the like, and materials
for footwear and the like.
EXAMPLES 1 17 AND COMPARATIVE EXAMPLES 1 15
The present invention will be described practically with reference
to examples below, but it is not intended that the present
invention is limited to those examples.
In the following examples, the modified block copolymers or the
hydrogenation products thereof and the modified block copolymer
compositions were measured for physical properties according to the
procedures as described under. In the examples, the modified block
copolymer and the modified block copolymer composition are
abbreviated simply "block copolymer" and "block copolymer
composition", respectively.
1. Characteristics of Block Copolymers and the Hydrogenation
Products Thereof
(1) Styrene Content
Styrene content was calculated from the absorbance intensity at 262
nm obtained with a UV spectrophotometer (HITACHI UV 200).
(2) Rate of Hydrogenation of Polybutadiene Moieties, Proportion of
Vinyl Bonds, and Proportion of the 1,2C.dbd.C Units
These were measured with a nuclear magnetic resonance apparatus
(DPX-400 available from BRUCKER Corporation).
(3) Weight Average Molecular Weight
GPC (Apparatus: LC1O made by SHIMADZU CORPORATION Column: Shimpac
GPC805+GPC804+GPC804+GPC803 made by SHIMADZU CORPORATION) was used
to make the measurement. Tetrahydrofuran was used as solvent, and
the measurement temperature was 35.degree. C. From the peak
molecular weight on a chromatogram, the weight average molecular
weight was determined according to a calibration curve which has
been obtained from the measurement of commercially available
standard polystyrenes (which was made by using the peak molecular
weights of standard polystyrenes).
(4) Proportion of Unmodified Block Copolymers
GPC Column filled with a silica-based gel has a characteristic to
adsorb the modified components, and this characteristic was made
use of to perform the measurement. For a sample solution containing
the modified block copolymers and the internal standard
polystyrenes having a low molecular weight, the proportion of the
modified block copolymers to the standard polystyrenes on the
chromatogram obtained in the above (3) was compared with the
proportion of the modified block copolymers to the standard
polystyrenes on the chromatogram which was obtained by GPC with a
silica column (Zorbax: a column made by DuPont Company) to
determine an amount of the components absorbed on the silica column
from the difference between both the proportions. A proportion of
the unmodified block copolymers is that of the copolymers which
were not adsorbed on the silica column.
(5) Content of Styrene Homopolymer Block (Block Ratio)
Styrene homopolymer blocks obtained by an oxidation decomposition
of copolymers according to the process as described above were
analyzed with a ultraviolet radiation spectrophotometer and the
block rate was determined by using the formula as follows. Block
ratio (%)=[(Weight percent of styrene homopolymer blocks in the
block copolymers before hydrogenation)/(Weight percent of the whole
styrene in the block copolymers before hydrogenation)].times.100 2.
Measurement of Physical Properties of the Block Copolymer
Composition (1) Transparency (Haze)
The block copolymer composition was molded under compression into a
sheet of a thickness of 2 mm as a test specimen which was measured
according to ASTM-D1003.
(2) Heat Resistance
The block copolymer composition was measured for the variation of
dynamic storage modulus (E') with temperature by using a DMA
spectrometer (983DMA available from DuPont Company) under the
conditions as described below to evaluate the heat resistance at an
inflection temperature in the high temperature region.
Thickness of the test specimen: 2 mm.
Length of a span: 16 mm.
Measurement temperature: 0.degree. C. to 200.degree. C.
Rate of temperature increase: 2.degree. C./min.
Measurement frequency mode: resonance frequency.
(3) Abrasion Resistance
The test specimen was measured for weight variation before and
after abraded 1000 times with a color fastness rubbing tester
(AB-301 available from TESTER SANGYO CO., LTD.)
(4) Processability
The block copolymer composition was melt-kneaded with twin-screw
open rollers at 200.degree. C., and evaluated for processability
from the conditions of winding around the rollers in three ratings
as follows:
.largecircle.: Good conditions of winding around the rollers
.DELTA.: incapable of winding around the rollers, but capable of
forming into sheet.
.times.: incapable of forming into sheet, and substantially
difficult to knead.
(5) JIS-A Hardness
The measurement was made according to JIS-K6301.
(6) Permanent Compression Set (%)
The measurement was made according to JIS-K-6301 (70.degree.
C..times.22 hours).
(7) Tensile Strength (MPa) and Tensile Elongation (%)
The measurement was made according to JIS-K-6251. The elongation
velocity was 500 mm/min.
(8) Flexural Strength (MPa)
The measurement was made according to ASTM-D790.
(9) Notched Izod Impact Strength (J/m)
The measurement was made according to JIS-K-7110.
(10) Average Particle Size in a Dispersion of Fillers (.mu.m)
The average particle size in a dispersion of fillers was measured
with a transmission electron microscope (TEM). TEM measurement
allowed the dispersion conditions of fillers to observe at a
magnification of 5000 to 100,000 and the number average particle
size in a dispersion was determined with an image analysis system
(Win ROOF, an image analysis system made by MITANI CORPORATION).
The number average particle size in a dispersion (d.sub.n) is
defined here as follows:
d.sub.n=.SIGMA.n.sub.id.sub.i/.SIGMA.n.sub.i(n.sub.i is the number
of particles having a particle size of d.sub.i)
The term "particle size" as used here refers to the diameter of an
equivalent circle having the same area as that of the particle.
3. Preparation of Hydrogenation Catalysts
In the preparation of the block copolymers as described below, the
hydrogenation catalysts which were used in the hydrogenation
reaction were prepared according to the following method:
(1) Hydrogenation Catalyst I
One liter of a dry purified cyclohexane was charged into a reaction
vessel which had been purged with nitrogen, to which 100 mmol of
bis(.eta..sup.5-cyclopentadienyl)titanium dichloride were added and
with sufficiently stirring a n-hexane solution containing 200 mmol
of trimethyl aluminum was added. The reaction was conducted for
about three days at room temperature.
(2) Hydrogenation Catalyst II
Two liters of a dry purified cyclohexane were charged into a
reaction vessel which had been purged with nitrogen, to which 40
mmol of bis(.eta..sup.5-cyclopentadienyl)titanium di-(p-tolyl) and
150 g of 1,2-polybutadiene having a molecular weight of about 1000
(a proportion of vinyl bonds: about 85%) were added and thereafter
a cyclohexane solution containing 60 mmol of n-butyl lithium was
added. Immediately after the reaction was conducted for 5 minutes
at room temperature, 40 mmol of n-butanol were added with stirring
and the content was preserved at room temperature.
4. Incorporated Components
In the examples under, the following compounds were employed as
components:
(1) Block Copolymers
The block copolymers were prepared by the procedure as described
hereinunder. The characteristics of the resulting block copolymers
are given in Tables 1 and 2.
(2) Fillers
Silica A: Precipitated silica (Sipernat 500LS: Secondary particle
size of 3.5 .mu.m; available from Degussa Huls AG)
Silica B: Highly dispersible anhydrous silica (HDK N20, available
from Wacker Asahikasei Silicone Co., Ltd.)
Silica C: Wet silica (Ultrasil VN3: Secondary particle size of 16
.mu.m; available from Degussa)
(3) Olefinic Polymers
Polypropylenes (PM801A, available from Montel SDK Co., Ltd.)
(4) Silane Coupling Agents
Bis-(3-triethoxysilylpropyl)-tetrasulfide (available from Degussa,
referred to as "Si69" hereinafter)
(5) Other Components
Rubber softening agents: Diana Process Oil PW-380, made by Idemitsu
Kosan Co., Ltd.
Polystyrene resin: Polystyrene 685, made by A & M STYRENE CO.,
LTD.
Polyphenylene ether resin: Poly(2,6-dimethyl-1,4-phenylene ether)
(Reduction viscosity, 0.54).
5. Preparation of Block Copolymers
1) Polymer 1
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 10
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
and tetramethylethylene diamine were added and after polymerizing
at 70.degree. C. for one hour, a solution containing 80 parts by
weight of a previously refined butadiene in cyclohexane (a
concentration of 20% by weight) was added and then the
polymerization was conducted at 70.degree. C. for one hour.
Moreover, a solution containing 10 parts by weight of styrene in
cyclohexane was added and then the polymerization was effected at
70.degree. C. for one hour. Thereafter,
tetraglycidyl-1,3-bisaminomethyl cyclohexane as a modifier
(referred to as Modifier M1 hereunder) was reacted in an equivalent
molar amount to that of the n-butyl lithium used in the
polymerization. The resulting modified block copolymer had a
styrene content of 20% by weight with a proportion of the viny
bonds in the polybutadiene moiety being of 50%.
To the modified block copolymer as obtained above, a hydrogenation
catalyst II was added in an amount of 100 ppm as Ti and the
hydrogenation reaction was carried out at a temperature of
65.degree. C. under a hydrogen pressure of 0.7 MPa for one hour.
Thereafter, methanol was added, then
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as
stabilizer in an amount of 0.3 part by weight based on 100 parts by
weight of the hydrogenated modified block copolymer. The resulting
hydrogenated modified block copolymer (Polymer 1) had the
properties as shown in Table 1. In this case, the proportion of the
unmodified block copolymer included in the Polymer 1 was 20% by
weight.
2) Polymer 2
Polyer 2 was prepared in the same procedure as that for Polyer 1,
except that the modifier was omitted. The properties of Polyer 2
are reported in Table 1.
3) Polymer 3
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 10
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
and tetramethylethylene diamine were added and after polymerizing
at 70.degree. C. for one hour, a solution containing 60 parts by
weight of a previously refined butadiene in cyclohexane (a
concentration of 20% by weight) was added and then the
polymerization was conducted at 70.degree. C. for one hour.
Moreover, a solution containing 10 parts by weight of styrene in
cyclohexane was added and then the polymerization was effected at
70.degree. C. for one hour. Thereafter, further a solution
containing 20 parts by weight of butadiene in cyclohexane was added
and then the polymerization was conducted at 70.degree. C. for one
hour. Then tetraglycidylmetaxylene diamine as a modifier (referred
to hereunder as Modifier M2) was reacted in an equivalent molar
amount to that of the n-butyl lithium used for the polymerization.
The resulting modified block copolymer had a styrene content of 20%
by weight with a proportion of the vinyl bonds in the polybutadiene
moiety being 50%.
To the modified block copolymer as obtained above, a hydrogenation
catalyst II was added in an amount of 100 ppm as Ti and the
hydrogenation reaction was carried out at a temperature of
65.degree. C. under a hydrogen pressure of 0.7 MPa for one hour.
Thereafter, methanol was added, then
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as
stabilizer in an amount of 0.3 part by weight based on 100 parts by
weight of the hydrogenated modified block copolymer. The resulting
hydrogenated modified block copolymer (Polymer 3) had the
properties as shown in Table 1. In this case, the proportion of the
unmodified block copolymer included in the Polymer 3 was 20% by
weight.
4) Polymer 4
Polyer 4 was prepared in the same procedure as that for Polyer 3,
except that the modifier was omitted. The properties of Polyer 4
are reported in Table 1.
5) Polymer 5
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 20
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
and tetramethylethylene diamine were added and after polymerizing
at 70.degree. C. for one hour, a solution containing 60 parts by
weight of a previously refined butadiene in cyclohexane (a
concentration of 20% by weight) was added and then the
polymerization was conducted at 70.degree. C. for one hour.
Moreover, a solution containing 20 parts by weight of styrene in
cyclohexane was added and then the polymerization was effected at
70.degree. C. for one hour. Thereafter, the Modifier M1 was reacted
in a 1/4 equivalent molar amount to that of the n-butyl lithium
used for the polymerization. The resulting modified block copolymer
had a styrene content of 40% by weight with a proportion of the
vinyl bonds in the polybutadiene moiety being 17%.
To the modified block copolymer as obtained above, methanol was
added to deactivate it, then
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate
was added as stabilizer in an amount of 0.3 part by weight based on
100 parts by weight of the modified block copolymer. The solution
of modified block copolymer in cyclohexane was subjected to steam
stripping to remove the cyclohexane therefrom so as to produce a
modified block copolymer (Polymer 5) which had the properties as
shown in Table 1. In this case, the proportion of the unmodified
block copolymer included in the Polymer 5 was 30% by weight.
6) Polymer 6
Polyer 6 was prepared in the same procedure as that for Polyer 5,
except that SiCl4 was employed in a 1/4 equivalent molar amount to
that of n-butyl lithium used in the polymerization instead of the
Modifier Ml. The properties of Polyer 6 are reported in Table
1.
7) Polymer 7
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 35
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
and tetramethylethylene diamine were added and after polymerizing
at 70.degree. C. for one hour, a solution containing 20 parts by
weight of a previously refined butadiene and 10 parts by weight of
styrene in cyclohexane (a concentration of 20% by weight) was added
and then the polymerization was conducted at 70.degree. C. for one
hour. Moreover, a solution containing 35 parts by weight of styrene
in cyclohexane was added and then the polymerization was effected
at 70.degree. C. for one hour. Thereafter,
N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propaneamine as
modifier (referred to hereinunder Modifier M3) was reacted in an
equivalent molar amount to that of the n-butyl lithium used for the
polymerization. The resulting modified block copolymer had a
styrene content of 80% by weight with a proportion of the vinyl
bonds in the polybutadiene moiety being 35%.
To the modified block copolymer as obtained above, a hydrogenation
catalyst II was added in an amount of 100 ppm as Ti and the
hydrogenation reaction was carried out at a temperature of
65.degree. C. under a hydrogen pressure of 0.7 MPa for one hour.
Thereafter, methanol was added, then
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as
stabilizer in an amount of 0.3 part by weight based on 100 parts by
weight of the hydrogenated modified block copolymer. The resulting
hydrogenated modified block copolymer (Polymer 7) had the
properties as shown in Table 1. In this case, the proportion of the
unmodified block copolymer included in the Polymer 7 was 40% by
weight.
8) Polymer 8
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 15
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
and tetramethylethylene diamine were added and after polymerizing
at 70.degree. C. for one hour, a solution containing 70 parts by
weight of a previously refined butadiene in cyclohexane (a
concentration of 20% by weight) was added and then the
polymerization was conducted at 70.degree. C. for one hour.
Moreover, a solution containing 15 parts by weight of styrene in
cyclohexane was added and then the polymerization was effected at
70.degree. C. for one hour. Thereafter, .gamma.-glycidoxypropyl
triemethoxysilane as modifier (referred to hereinunder as "Modifier
M4") was reacted in an equivalent molar amount to that of the
n-butyl lithium used for the polymerization. The resulting modified
block copolymer had a styrene content of 30% by weight with a
proportion of the vinyl bonds in the polybutadiene moiety being
40%.
To the modified block copolymer as obtained above, a hydrogenation
catalyst II was added in an amount of 100 ppm as Ti and the
hydrogenation reaction was carried out at a temperature of
65.degree. C. under a hydrogen pressure of 0.7 MPa for one hour.
Thereafter, methanol was added, then
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as
stabilizer in an amount of 0.3 part by weight based on 100 parts by
weight of the hydrogenated modified block copolymer. The solution
of hydrogenated modified block copolymer in cyclohexane was
subjected to steam stripping to remove the cyclohexane so as to
produce a hydrogenated modified block copolymer (Polymer 8) which
had the properties as shown in Table 1. In this case, the
proportion of the unmodified block copolymer included in the
Polymer 8 was 25% by weight.
9) Polymer 9
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 8
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
and tetramethylethylene diamine were added and after polymerizing
at 70.degree. C. for one hour, a solution containing 85 parts by
weight of a previously refined isoprene in cyclohexane (a
concentration of 20% by weight) was added and then the
polymerization was conducted at 70.degree. C. for one hour.
Moreover, a solution containing 7 parts by weight of styrene in
cyclohexane was added and then the polymerization was effected at
70.degree. C. for one hour. Thereafter, the Modifier Ml was reacted
in a 1/4 equivalent molar amount to that of the n-butyl lithium
used for the polymerization. The resulting modified block copolymer
had a styrene content of 15% by weight with a proportion of the
vinyl bonds in the polyisoprene moiety being 30%.
To the modified block copolymer as obtained above, methanol was
added to deactivate it, then
2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenylacrylate
was added as stabilizer in an amount of 0.3 part by weight based on
100 parts by weight of the modified block copolymer. The solution
of the modified block copolymer in cyclohexane was subjected to
steam stripping to remove the cyclohexane so as to produce a
modified block copolymer (Polymer 9) which had the properties as
shown in Table 1. In this case, the proportion of the unmodified
block copolymer included in the Polymer 9 was 30% by weight.
10) Polymer 10
Polyer 10 was prepared in the same procedure as that for Polyer 1,
except that 1,3-dimethyl-2-imidazolidinone (referred to M5
hereinafter) was employed as a modifier. The properties of Polyer
10 are reported in Table 1.
TABLE-US-00001 TABLE 1 Pro- Weight portion Average Styrene of Viny
Molecular Content bonds Weight Types of Hydrogenation Sample No.
(wt. %) (%) (.times.10,000) Modifier Rate (%) Polymer 1 20 50 8 M1
98 Polymer 2 20 50 8 None 98 Polymer 3 20 50 8 M2 98 Polymer 4 20
50 8 None 98 Polymer 5 40 17 15 M1 0 Polymer 6 40 17 15 SiCl.sub.4
0 Polymer 7 80 35 20 M3 98 Polymer 8 30 40 10 M4 98 Polymer 9 15 30
18 M1 0 Polymer 10 20 50 8 M5 98
11) Polymer 11
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 14.7
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
and tetramethylethylene diamine were added and after polymerizing
at 70.degree. C. for one hour, a solution containing 72 parts by
weight of a previously refined butadiene in cyclohexane (a
concentration of 20% by weight) was added and then the
polymerization was conducted at 70.degree. C. for one hour.
Moreover, a solution containing 13.3 parts by weight of styrene in
cyclohexane was added and then the polymerization was effected at
70.degree. C. for one hour. Thereafter, the Modifier M5 was reacted
in an equivalent molar amount to that of the n-butyl lithium used
for the polymerization. The resulting modified block copolymer had
a styrene content of 28% by weight with a proportion of the vinyl
bonds in the polybutadiene moiety being 38%.
To the modified block copolymer as obtained above, a hydrogenation
catalyst II was added in an amount of 100 ppm as Ti and the
hydrogenation reaction was carried out at a temperature of
65.degree. C. under a hydrogen pressure of 0.7 MPa for one hour.
Thereafter, methanol was added, then
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as
stabilizer in an amount of 0.3 part by weight based on 100 parts by
weight of the block copolymer. Then the resulting solution of
hydrogenated modified block copolymer in cyclohexane was heated to
remove the cyclohexane so as to produce a hydrogenated modified
block copolymer (Polymer 11). The analysis of the polymer 11 showed
the results as shown in Table 2. In this case, the proportion of
the unmodified block copolymer included in the Polymer 11 was 20%
by weight.
12) Polymer 12
Polyer 12 was prepared in the same procedure as that for Polyer 11,
except that the modifier was not employed. The properties of Polyer
12 are reported in Table 2.
13) Polymer 13
Polyer 13 was prepared in the same procedure as that for Polyer 11,
except that SiCl4 was employed in a 1/4 equivalent molar amount to
that of the n-butyl lithium used in the polymerization instead of
the Modifier M5. The properties of Polyer 13 are reported in Table
2.
14) Polymer 14
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 20.5
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
and tetramethylethylene diamine were added and after polymerizing
at 70.degree. C. for one hour, a solution containing 61 parts by
weight of a previously refined butadiene in cyclohexane (a
concentration of 20% by weight) was added and then the
polymerization was conducted at 70.degree. C. for one hour.
Moreover, a solution containing 18.5 parts by weight of styrene in
cyclohexane was added and then the polymerization was effected at
70.degree. C. for one hour. Thereafter, the Modifier Ml was reacted
in an equivalent molar amount to that of the n-butyl lithium used
for the polymerization. The resulting modified block copolymer had
a styrene content of 39% by weight with a proportion of the vinyl
bonds in the polybutadiene moiety being 37%.
To the block copolymer as obtained above, a hydrogenation catalyst
II was added in an amount of 100 ppm as Ti and the hydrogenation
reaction was carried out at a temperature of 65.degree. C. under a
hydrogen pressure of 0.7 MPa for one hour. Thereafter, methanol was
added, then octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate
was added as stabilizer in an amount of 0.3 part by weight based on
100 parts by weight of the block copolymer. Then the resulting
solution of hydrogenated modified block copolymer in cyclohexane
was heated to remove the cyclohexane so as to produce a
hydrogenated modified block copolymer (Polymer 14). The analysis of
the polymer 14 showed the results as shown in Table 2. In this
case, the proportion of the unmodified block copolymer included in
the Polymer 14 was 25% by weight.
15) Polymer 15
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 17.8
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
and tetramethylethylene diamine were added and after polymerizing
at 70.degree. C. for one hour, a solution containing 66 parts by
weight of a previously refined butadiene in cyclohexane (a
concentration of 20% by weight) was added and then the
polymerization was conducted at 70.degree. C. for one hour.
Moreover, a solution containing 16.2 parts by weight of styrene in
cyclohexane was added and then the polymerization was effected at
70.degree. C. for one hour. Thereafter, the Modifier M4 was reacted
in an equivalent molar amount to that of the n-butyl lithium used
for the polymerization. The resulting modified block copolymer had
a styrene content of 34% by weight with a proportion of the vinyl
bonds in the polybutadiene moiety being 42%.
To the modified block copolymer as obtained above, a hydrogenation
catalyst II was added in an amount of 100 ppm as Ti and the
hydrogenation reaction was carried out at a temperature of
65.degree. C. under a hydrogen pressure of 0.7 MPa for one hour.
Thereafter, methanol was added, then
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as
stabilizer in an amount of 0.3 part by weight based on 100 parts by
weight of the hydrogenated modified block copolymer. Then the
resulting solution of hydrogenated modified block copolymer in
cyclohexane was heated to remove the cyclohexane so as to produce a
hydrogenated modified block copolymer (Polymer 15). The analysis of
the Polymer 15 showed the results as shown in Table 2. The
proportion of the unmodified block copolymer included in the
Polymer 15 was 25% by weight.
16) Polymer 16
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 35.1
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
and tetramethylethylene diamine were added and after polymerizing
at 70.degree. C. for one hour, a solution containing 33 parts by
weight of a previously refined butadiene in cyclohexane (a
concentration of 20% by weight) was added and then the
polymerization was conducted at 70.degree. C. for one hour.
Moreover, a solution containing 31.9 parts by weight of styrene in
cyclohexane was added and then the polymerization was conducted at
70.degree. C. for one hour. Thereafter, the Modifier M5 was reacted
in an equivalent molar amount to that of the n-butyl lithium used
for the polymerization. The resulting modified block copolymer had
a styrene content of 67% by weight with a proportion of the vinyl
bonds in the polybutadiene moiety being 18%.
To the modified block copolymer as obtained above, a hydrogenation
catalyst II was added in an amount of 100 ppm as Ti and the
hydrogenation reaction was carried out at a temperature of
65.degree. C. under a hydrogen pressure of 0.7 MPa for one hour.
Thereafter, methanol was added, then
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as
stabilizer in an amount of 0.3 part by weight based on 100 parts by
weight of the hydrogenated modified block copolymer. Then the
resulting solution of hydrogenated modified block copolymer in
cyclohexane was heated to remove the cyclohexane so as to produce a
hydrogenated modified block copolymer (Polymer 16). The analysis of
the polymer 16 showed the results as shown in Table 2. In this
case, the proportion of the unmodified block copolymer included in
the Polymer 16 was 30% by weight.
17) Polymer 17
Polyer 17 was prepared in the same procedure as that for Polyer 16,
except that the hydrogenation catalyst I was added in an amount of
100 ppm as Ti and the hydrogenation reaction was conducted at a
temperature of 65.degree. C. under a hydrogen pressure of 0.7 MPa
with a hydrogenation rate being 60%. The properties of Polyer 17
are shown in Table 2.
18) Polymer 18
Into an autoclave equipped with a stirrer and a jacket after it was
cleaned, dried and purged with nitrogen, a solution containing 20
parts by weight of a previously purified styrene in cyclohexane (a
concentration of 20% by weight) was charged. Then n-butyl lithium
was added and after polymerizing at 70.degree. C. for one hour, a
solution containing 30 parts by weight of a previously refined
butadiene in cyclohexane (a concentration of 20% by weight) was
added and then the polymerization was conducted at 70.degree. C.
for one hour. Moreover, a solution containing 50 parts by weight of
styrene in cyclohexane was added and then the polymerization was
effected at 70.degree. C. for one hour. The resulting block
copolymer had a styrene content of 70% by weight with a proportion
of the vinyl bonds in the polybutadiene moiety being 11%. Moreover,
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate was added as
stabilizer in an amount of 0.3 part by weight based on 100 parts by
weight of the block copolymer. Then the resulting solution of block
copolymer in cyclohexane was heated to remove the cyclohexane so as
to produce a block copolymer (Polymer 18). The analysis of the
Polymer 18 showed the results as shown in Table 2.
19) Polymer 19
Polyer 19 was prepared in the same procedure as that for Polyer 11,
except that the amount of n-butyl lithium was controled to reduce
the molecular weight. The properties of Polyer 19 are shown in
Table 2.
20) Polymer 20
Polyer 20 was prepared in the same procedure as that for Polyer 19,
except that the modifier was not employed. The properties of Polyer
20 are shown in Table 2.
TABLE-US-00002 TABLE 2 Block ratio Proportion Styrene Proportion
Weight Average of styrene Hydrogenation of 1,2C.dbd.C Content of
Viny Molecular Types of homopolmer Rate units Sample No. (wt. %)
bonds (%) Weight (.times.10,000) Modifier (%) (%) (%) Polymer 11 28
38 18 M5 99 98 0 Polymer 12 28 38 18 None 99 98 0 Polymer 13 28 38
38 SiCl.sub.4 99 98 0 Polymer 14 39 37 40 M1 93 98 0 Polymer 15 34
42 25 M4 91 98 0 Polymer 16 67 18 8 M5 91 98 0 Polymer 17 67 18 8
M5 91 60 0.5 Polymer 18 70 11 11 None 90 0 12 Polymer 19 28 38 8 M5
99 98 0 Polymer 20 28 38 8 None 99 98 0
Example 1
A solution of Polymer 1 in cyclohexane was mixed with silica A in
an amount of 5 parts by weight based on 100 parts by weight of
Polymer 1. A part of this mix solution was sampled and left to
stand for one day and night. Silica A was still uniformly finely
dispersed and little silica was separated to precipitate from the
mix solution. Thus it could be confirmed that Polymer 1 and silica
A were intimately unified to form a composite condition.
Next, the mix solution of Polymer 1 and silica A was heated to
remove the cyclohexane so as to produce a block copolymer
composition. The physical properties of the resulting composition
are shown in Table 3.
Comparative Example 1
Similarly to Example 1, to a solution of Polymer 2, silica A was
added to produce a mixture. A part of this solution was sampled and
left to stand for one day and night. As a result, the silica A was
precipitated and no composite condition as in Example 1 could be
developed.
Next, the mix solution of Polymer 2 and silica A as above was
heated to remove the cyclohexane so as to produce a block copolymer
composition. The physical properties of the resulting composition
are shown in Table 3.
Comparative Examples 2 and 3
A block copolymer composition having an amount of silica A
incorporated lower than the range of the amount in formulation
defined in the present invention (Comparative Example 2), and a
block copolymer composition having an amount of silica A
incorporated higher than said range (Comparative Example 3) were
prepared in the same procedure as in Example 1. The resulting
compositions have physical properties as shown in Table 3.
Example 2
A solution of Polymer 3 in cyclohexane was mixed with silica A in
an amount of 5 parts by weight based on 100 parts by weight of
Polymer 3. A part of this solution was sampled and left to stand
for one day and night. Silica A was still uniformly finely
dispersed and little silica A was separated to precipitate from the
solution. Thus it could be confirmed that Polymer 3 and silica A
were intimately unified to form a composite condition.
Next, the mix solution of Polymer 3 and silica A as described above
was heated to remove the cyclohexane so as to produce a block
copolymer composition. The physical properties of the resulting
composition are shown in Table 3.
Moreover, the examination of the abrasion resistance of this
composition showed that an abrasion quantity was 14 mg.
Comparative Example 4
Similarly to Example 2, to a solution of Polymer 4 in cyclohexane,
silica A was added to produce a mixture. A part of this solution
was sampled and left to stand for one day and night. As a result,
the silica A was precipitated and no composite condition as in
Example 2 could be developed.
Next, the mix solution of Polymer 4 and silica A as above was
heated to remove the cyclohexane so as to produce a block copolymer
composition. The physical properties of the resulting composition
are shown in Table 3.
Moreover, the examination of the abrasion resistance of this
composition showed that an abrasion quantity was 25 mg.
Example 3
100 parts by weight of Polymer 5 and 30 parts by weight of silica B
were mixed in a twin screw extruder with two screws of a L/D 34 and
30 mm .phi. rotating in the same direction to produce a block
copolymer composition. The extruder was operated at an extrusion
temperature of 210.degree. C., and a revolution of 200 rpm. The
resulting composition had a haze of 55%.
Comparative Example 5
With Polymer 6, a block copolymer composition was obtained in the
same procedure as in Example 3. The resulting composition had a
haze of 80% so that it was inferior in transparency to the
composition of Example 3.
Example 4
A solution of Polymer 7 in cyclohexane was mixed with silica B in
an amount of 5 parts by weight based on 100 parts by weight of
Polymer 7. A part of this solution was sampled and left to stand
for one day and night. Silica B was still uniformly finely
dispersed and little silica B was separated to precipitate from the
solution. Thus it could be confirmed that Polymer 7 and silica B
were intimately unified to form a composite condition.
Example 5
A solution of Polymer 8 in cyclohexane was mixed with silica C in
an amount of 10 parts by weight based on 100 parts by weight of
Polymer 8. A part of this solution was sampled and left to stand
for one day and night. Silica C was still uniformly finely
dispersed and little silica C was separated to precipitate from the
solution. Thus it could be confirmed that Polymer 8 and silica C
were intimately unified to form a composite condition.
Example 6
A solution of Polymer 9 in cyclohexane was mixed with silica A in
an amount of 20 parts by weight based on 100 parts by weight of
Polymer 9. A part of this solution was sampled and left to stand
for one day and night. Silica A was still uniformly finely
dispersed and little silica A was separated to precipitate from the
solution. Thus it could be confirmed that Polymer 9 and silica A
were intimately unified to form a composite condition.
Example 7
A solution of Polymer 10 in cyclohexane was mixed with silica A in
an amount of 5 parts by weight based on 100 parts by weight of
Polymer 10. A part of this solution was sampled and left to stand
for one day and night. Silica A was still uniformly finely
dispersed and little silica A was separated to precipitate from the
solution. Thus it could be confirmed that Polymer 10 and silica A
were intimately unified to form a composite condition.
TABLE-US-00003 TABLE 3 Physical Properties of Composition
Components of Composition Heat Component (1) Component (2)
Transparency resistance Content Content Haze .DELTA. Inflection
Type (wt. parts) Type (wt. parts) (%) Temp. (.degree. C.)
processability Example 1 Polymer 1 100 Silica A 5 45 175
.largecircle. Comp. Example 1 Polymer 2 100 Silica A 5 77 130
.largecircle. Comp. Example 2 Polymer 1 100 Silica A 0.1 5 100
.largecircle. Comp. Example 3 Polymer 1 100 Silica A 60 not
producing good shapes X Example 2 Polymer 3 100 Silica A 5 43 160
.largecircle. Comp. Example 4 Polymer 4 100 Silica A 5 75 125
.largecircle.
Examples 8 and 9
100 parts by weight of Polymer 11 and a rubber softening agent
(PW-380) were melt-kneaded in a twin screw extruder with screws of
30 mm c at 230.degree. C. and at compositions as shown in Table 4.
Thereafter the silica A or C in an amount indicated in Table 4 as
the component (2), a polypropylene resin in an amount indicated in
Table 4 as the component (3), and 0.88 part by weight of
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate as
stabilizer were added. The resulting mixture was melt-kneaded in a
twin screw extruder with screws of 25 mm .phi. at 230.degree. C. to
produce block copolymer compositions. The physical properties of
the resulting compositions are shown in Table 4.
Comparative Example 6
Block copolymer compositions were produced in the same procedure as
that in Examples 8 and 9, except that no silica was incorporated.
The physical properties of the resulting compositions are shown in
Table 4.
Comparative Example 7
Block copolymer compositions were produced in the same procedure as
that in Examples 8 and 9, except that silica B was incorporated in
an amount of 80 parts by weight. The physical properties of the
resulting compositions are shown in Table 4.
Comparative Example 8
Block copolymer compositions were produced in the same procedure as
that in Example 8 by using Polymer 12. The physical properties of
the resulting compositions are shown in Table 4.
Comparative Example 9
Block copolymer compositions were produced in the same procedure as
that in Example 8 by using Polymer 13. The physical properties of
the resulting compositions are shown in Table 4.
Example 10
100 parts by weight of Polymer 14 and 100 parts by weight of a
rubber softening agent (PW-380) were melt-kneaded in a twin screw
extruder with screws of 30 mm .phi. at 230.degree. C. Thereafter
the silica A in an amount of 15 parts by weight as the component
(2), a polypropylene resin in an amount of 34 parts by weight as
the component (3), and 0.88 part by weight of
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate as
stabilizer were added. The resulting mixture was melt-kneaded in a
twin screw extruder with screws of 25 mm .phi. at 230.degree. C. to
produce a block copolymer composition. The physical properties of
the resulting composition are shown in Table 4.
Example 11
100 parts by weight of Polymer 15 and 100 parts by weight of a
rubber softening agent (PW-380) were melt-kneaded in a twin screw
extruder with screws of 30 mm .phi. at 230.degree. C. to produce a
mixture. Thereafter, to the mixture, the silica A in an amount of
15 parts by weight as the component (2), a polypropylene resin in
an amount of 34 parts by weight as the component (3), and 0.88 part
by weight of octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate
as stabilizer were added, and the whole was melt-kneaded in a twin
screw extruder with screws of 25 mm .phi. at 230.degree. C. to
produce a block copolymer composition. The physical properties of
the resulting composition are shown in Table 4.
TABLE-US-00004 TABLE 4 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Comp. Ex. 6 Comp.
Ex. 7 Comp. Ex. 8 Comp. Ex. 9 Composition Polymer 11 100 100 -- --
100 100 -- -- (parts by Polymer 12 -- -- -- -- -- -- 100 -- Weight)
Polymer 13 -- -- -- -- -- -- -- 100 Polymer 14 -- -- 100 -- -- --
-- -- Polymer 15 -- -- -- 100 -- -- -- -- Silica A 15 -- 15 15 --
-- 15 15 Silica B -- -- -- -- -- 80 -- -- Silica C -- 50 -- -- --
-- -- -- Polypropylene 34 30 34 34 34 26 34 34 Rubber Softening
Agent 100 136 100 100 88 165 100 100 Hardness (JIS A) 62 59 63 63
63 59 62 63 Permanent Compression Set (%) 29 26 28 29 37 27 35 35
Tensile Break Strength (MPa) 13 8 14 14 13 6 15 15 Processability
.largecircle. .largecircle. .largecircle. .largecircle. .la-
rgecircle. X .largecircle. X Average particle size in a 0.2 0.2 0.1
0.2 0.3 0.4 0.4 0.4 dispersion of fillers (.mu.m)
Examples 12 and 13
100 parts by weight of Polymer 11 and 100 parts by weight of a
rubber softening agent (PW-380) were melt-kneaded in a twin screw
extruder with screws of 30 mm .phi. at 230.degree. C. Thereafter
the silica 2 in an amount of shown in Table 5 as the component (2),
a polypropylene resin in an amount shown in Table 5 as the
component (3), 3 parts by weight of polystyrene resin, 7 parts by
weight of a polyphenylene ether resin, and 0.88 part by weight of
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate as
stabilizer were added. The resulting mixture was melt-kneaded in a
twin screw extruder with screws of 25 mm .phi. at 270.degree. C. to
produce a block copolymer composition. The physical properties of
the resulting composition are shown in Table 5.
Comparative Example 10
A block copolymer composition was produced in the same procedure as
that in Example 12, except that Polymer 12 was used. The physical
properties of the resulting composition are shown in Table 5.
Comparative Example 11
A block copolymer composition was produced in the same procedure as
that in Example 12 using Polymer 18. The physical properties of the
resulting composition are shown in Table 5.
TABLE-US-00005 TABLE 5 Ex. Ex. Comp. 12 13 Ex. 10 Comp. Ex. 11
Composition Polymer 11 100 100 -- -- (parts by Polymer 12 -- -- 100
-- weight) Polymer 18 -- -- -- 100 Silica B 15 40 15 15
Polypropylene 34 30 34 34 Rubber 100 136 100 100 Softening Agent
Polystyrene 3 3 3 3 Polyphenylene 7 7 7 7 ether Hardness (JIS A) 62
60 62 Gellation & Permanent Compression Set (%) 30 26 37
decomposition Average particle size in a 0.3 0.2 0.3 dispersion of
fillers (.mu.m)
Examples 14
100 -parts by weight of Polymer 16, 10 parts by weight of silica A
as the component (2), 271 parts by weight of polypropylene resin
and 834 parts by weight of polystyrene resin as the component (3),
and 0.88 part by weight of
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate as
stabilizer were added and the resulting mixture was melt-kneaded in
a twin screw extruder with screws of 25 mm .phi. at 230.degree. C.
to produce a block copolymer composition. The physical properties
of the resulting composition are shown in Table 6.
Example 15
A block copolymer composition was produced in the same procedure as
that in Example 14 using Polymer 17. The physical properties of the
resulting composition are shown in Table 6.
Comparative Example 12
A block copolymer composition was produced in the same procedure as
that in Example 15, except that the silica was not used. The
physical properties of the resulting composition are shown in Table
6.
Comparative Example 13
A block copolymer composition was produced in the same procedure as
that in Example 15, except that Polymer 18 was used, but the silica
was not used. The physical properties of the resulting composition
are shown in Table 6.
TABLE-US-00006 TABLE 6 Comp. Comp. Ex. 14 Ex. 15 Ex. 12 Ex. 13
Composition Polymer 16 100 -- -- -- (parts by Polymer 17 -- 100 100
-- weight) Polymer 18 -- -- -- 100 Silica A 10 10 -- --
Polypropylene 271 271 271 271 Polystyrene 834 834 834 834 flexural
strength (MPa) 82 82 73 71 Izod impact strength (J/m) 157 158 149
149
Examples 16
100 parts by weight of Polymer 19, 10 parts by weight of silica C
as the component (2), and 0.88 part by weight of
octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate as
stabilizer were added and the resulting mixture was melt-kneaded in
a twin screw extruder with screws of 25 mm .phi. at 220.degree. C.
to produce a block copolymer composition. The physical properties
of the resulting composition are shown in Table 7.
Example 17
A block copolymer composition was produced in the same procedure as
that in Example 16, except that Si69 was incorporated in an amount
of 10% by weight based on the silica C. The physical properties of
the resulting composition are shown in Table 7.
Comparative Example 14
A block copolymer composition was produced in the same procedure as
that in Example 16 using Polymer 20. The physical properties of the
resulting composition are shown in Table 7.
Comparative Example 15
A block copolymer composition was produced in the same procedure as
that in Example 17 using Polymer 20. The physical properties of the
resulting composition are shown in Table 7.
TABLE-US-00007 TABLE 7 Ex. Ex. Comp. Comp. 16 17 Ex. 14 Ex. 15
Composition Polymer 19 100 100 -- -- (parts by weight) Polymer 20
-- -- 100 100 (parts by weight) Silica C 10 10 10 10 (parts by
weight) Si69 (% by weight/silica) -- 10 -- 10 Tensile strength
(MPa) 28 32 17 17 Tensile elongation (%) 590 590 610 610
From the results of Examples 1 to 17 and Comparative Examples 1 to
15 as described above, it can be seen that the block copolymer
composition of the present invention is excellent in heat
resistance, mechanical strength, transparency, abrasion resistance,
and processability and that the block copolymer composition having
further an olefinic polymer incorporated is excellent in mechanical
strength, permanent compression set, impact resistance, and
processability.
Industrial Applicability
The modified block copolymer composition of the present invention
comprising specific amounts of (1) a specifically structured
modified block copolymer containing specific functional groups or
the hydrogenation products thereof and (2) at least one of fillers
selected from the group consisting of silica-based inorganic
fillers, metal oxides, and metal hydroxides is excellent in heat
resistance, mechanical strength, transparency, abrasion resistance,
and processability. Moreover, incorporating an olefinic polymer
into the composition as above can further improve the mechanical
strength, permanent compression set, impact resistance, and
processability.
By making use of the characteristics as described above, the
modified block copolymer composition of the present invention
allows for processing into various shaped articles by injection
molding, extrusion molding and the like. Thus, it can be used for
automobile parts, domestic electrical appliances, wire covers,
medical parts, footwears, miscellaneous goods, and the like.
* * * * *